Fragrance materials containing 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclo-hexen-1-yl)-2-butanol, and/or acetals thereof, and methods for producing same

ABSTRACT

Methods for preparing perfume compositions and ingredients for perfume compositions by including therein 4-(2,6,6-trimethyl-1,3cyclohexadien-1-yl)-2-butanol or 4-(6,6-dimethyl-2-methylene-3cyclohexen-1-yl)-2-butanol or acetals thereof to produce in perfumes, a leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone character with a slight musky nuance.

United States Patent [191 Mookherjee et al.

Edward J. Shuster, Brooklyn, both of NY.

International Flavors & Fragrances Inc., New York, NY.

Filed: Mar. 24, 1975 Appl. No.: 561,188

Related US. Application Data Continuation-impart of Ser. No. 461,704, April 17, 1974, Pat. No. 3,899,597.

Assignee:

US. Cl 252/522; 260/617 R; 260/6755 Int. Cl. A61K 7/46; C1 1B 9/00 Field of Search 252/522; 260/675.5

References Cited UNITED STATES PATENTS 12/1942 Kremers 260/488 R Dec. 23, 1975 2,843,631 7/1958 lsler et a1. 260/488 A 2,877,271 3/1959 Kaiser et al 426/538 3,222,187 12/1965 Winter 426/538 3,436,421 4/1969 Rowland 260/587 3,872,031 3/1975 Mookherjee et a1 252/522 OTHER PUBLICATIONS Artander Perfume and Flavor Chemicals Vol. 1 & 2 (1969), Compound Nos. 1775 and Ionols, lonones.

Kruk and De Boer, Recueil: Vol. 87 (1968), pp. 641-654.

Primary Examinerl-lerbert Levine Assistant ExaminerG. E. Schmitkons Attorney, Agent, or FirmArthur L. Liberman, Esq.; Harold Haidt, Esq.

[57] ABSTRACT Methods for preparing perfume compositions and ingredients for perfume compositions by including therein 4-( 2,6,6-trimethyl- 1 ,3-cyclohexadien- 1 -yl )-2- butanol or 4-( 6,6-dimethyl-2-methy1ene-3-cyclohexen- 1-y1)-2-butanol or acetals thereof to produce in perfumes, a leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone character with a slight musky nuance.

12 Claims, No Drawings FRAGRANCE MATERIALSrCONTAINING 4-(2,6,6-TRIMETHYL-l,3-CYCLOHEXADIEN-1-- YL)-2-BUTANOL AND/OR 4-(6,6-DIMETHYL-2-METHYLENE-3-CYCLO-HEX- 5 EN-1-YL)-2-BUTANOL, AND/OR. ACETALS THEREOF, AND METHODS FOR PRODUCING SAME This application is a continuation-in-part of US. 7 Application Letters at 461,704 filed 10 is also produced in this process as a bi-product thereof on April 1974, now P (B.P. 65C at 0.15 mm Hg. pressure). 4-(2,6,6-trimeth- 1-l,3-c clohexadien-l- 1)-2-butanone' is also shown to BACKGROUNDQF THE. INVENTION be a bi product in the cyclization of ionone to beta The present invention relates to novel methods and ionone b K k and De Boer in Volume 87 Recueil compositions using y y 15 (1968) pp. 641-654 as an intermediate in preparing -yD- n I and/0f y y- 1 other perfumery compounds. The compound having lene-3-cyclohexen-1-y1)-2-butanol and/or 4-(2,6,6: the structure: trimethyl-l,3-cyclohexadien-l y1)-2-buty1 acetate and- /or 4-(6,6-dimethyl-2-methylene-3 cyclohexen-1-yl)-2- butyl acetate to alter the aroma of perfume composi- 20 I tions and perfumed articles. There has been considerable work performed relating to substances which can be used to impart aromas to various perfumery materials. These substances are used to diminish natural materials some of which may be in short supply and provide more uniform properties in finished products. Leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone and musky aromas are particularly desirable in perfume composiis disclosed in Japanese Pat. No. 7121,015 (Sakan and tions and perfumed articles. lsoe) issued June 14, 1971.

The fragrance material having the structure: Japanese Pat. No. 7404,391 discloses a synthesis of the compound having the structure:

from a compound having the structure:

is disclosed in British Pat. No. 1 305,621 issued on Feb. H I 7,1973.

4-(2,6,6-trimethyl-1,3-cyclohexadien-1-y1)-2-butanone having the structure:

Q This patent indicates that the synthesized compound 1 can improve the aroma and quality of distilled spirits.

M Compounds of the structures:

H OH

. and may be synthesized according to the technique of Wolf I D Y and Zink, Volume 56, Helvetica Chimica Acta., Fasc 3 (1973) pp. 1062-1066, or according to Examples I and II of Rowland, US. Pat. No. 3,436,421 issued on Apr. 1, 1969 by means of bromination of a-dihydroionone 5 followed by debromination. 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanone having the structure: I w:

are indicated to be intermediates in the synthesis gamma-dihydroionone by Stoll, I-Ielv. Chim. Acta, 38, 1587 (1955) and British Pat. No. 794,416. The synthesis of the compound having the structure:

is disclosed by Naves and Bachmann, Helv. Chim. Acta, 26, 2151 (1943).

Sato and Mashima, Tetrahedron Letters No. 22, Page 1803 (1969) discloses the synthesis of theaspirone from the material having the structure:

O /H\ i but no odor qualities of this acetate are set forth therein. Demole et al., Helv. Chim. Acta, 53, 541 (1970) discloses the synthesis of the alcohol having the structure: I

Arctander, Perfume and Flavor Chemicals (Aroma Chemicals), 1969 discloses in Vol. I at 1775 betaionol having the structure:

HZC H C C-C H=C H-CH -CH c OH H3C CH3 as having a :sweet, oily-herbaceous, warm odor with floral-balsamic undertones some resemblance to Labdanum notes" Arctander further states that this secondary alcohol has been suggested for use in perfume compositions as a a modifier in various types of floral and non-floral fragrances. It blends well with Labdanum, Lavender, Lavandin, Clary Sage, etc. and it has a refreshing effect upon Rose types. It performs pleasantly with the eliphatic aldehydes into refreshing notes varying from Pine to Rose, and it was at one time used in several types of detergent fragrances. It is produced by reduction of betaionone with sodium alcoholate or by Meerwein-Ponndorf-Verley reduction.

THE INVENTION It has now been discovered that novel aroma imparting compositions having leathery, green, orris, seashore, mimosa, clary sage, woody, fruity, ionone character with a slight musky nuance characteristics may be provided by the utilization of 4-(2,6,6-trimethyl-l ,3- cyclohexadien-l-yl)-2-butanol and/or 4-(6,6-dimethyl- Z-methylene-3-cyclohexen-l-yl)-2-butanol and/or acetates thereof having the generic structure:

wherein R is acetyl or hydrogen and wherein one of the dashed lines represents a carbon-carbon double bond, and the other dashed line represents a carbon-carbon single bond. Thus, the 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanol and/or acetate thereof of our invention are capable of supplying aroma notes usually lacking in many perfumery materials, e.g., orris" and clary sage.

The 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2- butanol and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/or acetates thereof may be prepared by first forming dihydro-a-ionol from dihydro-a-ionone according to the following reaction:

l Ll Dlethyl ether The reaction is preferably carried out in an inert solvent such as diethyl ether at reflux temperatures, e.g., theboiling point of the solvent at atmospheric pressure.

The dihydro-a-ionol is then esterified via normal 5 6 esterification procedures according to the following The resulting product, consisting of 70-90% cyclohexreaction: adiene derivative and 30-10% of methylen'e-cyclohex- O ll to form the acetate which is, in turn, dehydrogenated, ene derivative may be used as a perfumery ingredient, using quinoline, preferably in an inert solvent such as as-is or it may be separated (e.g., using gas-liquid chloroform, at temperatures of the order of 5 C up to chromatography techniques) or it may be saponified to +l0C at atmospheric pressure, according to the folthe corresponding alcohol mixture using standard salowing reaction: ponification techniques thus:

I O r t O r i i I" O The saponification is carried using a base (e.g., KOH one NaOH) preferably in.-an alcohol solvent medium (e. g.,=;.

ethanol) at ambient conditions (although temperatures of 50C-60C will cause the saponification' 'reaction to process more rapidly). F

The resulting product, consisting of 70-90% cyclohexadiene derivative and 30-10% methylene cyclohexene derivative may be used in perfumery "a s-is or it may be separated (e.g., using gas-liquid chromatogra phy techniques).

4-(2,6,6-trimethyl-l ,3-cyclohexadien-1-yl)-2- butanol and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanoland/or 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butyl acetate and/or4-(6,6-'

dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butyl 'acedeodorants, hand lotions and sunscreensj'pow'ders such astales, dusting powde'rs, face powders and thelike.

When used as an olfactory component of a perfumed "article as little as l'parts per million of the 4-(2,6,6-

tate and an auxiliary perfume ingredient including, for example, alcohols, aldehydes, nitriles, esters, cyclic evaporation; and (d) topnotes which are usually low boiling fresh smelling materials.

In perfume compositions, the individual component will contribute its particular olfactory characteristics but the over-all effect of the perfume composition will be the sum of the effects of each of the ingredients. Thus, 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-yl)-2- butanol and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/or 4-(2,6,6-trimethyla l,3-cyclohexadien-l-yl)-2-butyl acetate a'nd/or 4'-'(6,6-

dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate can be used to alter the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of the 4-(2,6, 6-trimethyl-l,3-cyclohexadien-l -yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanol and/or 4-(2,6,6- trimethyl-l ,3-cyclohexadien-l-yl)-2-butyl acetate and- /or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-lyl)-2- butyl acetate of our invention which will be effective in perfume compositions depend on many factors including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.05% or 4-(2,6,6- trimethyl-l ,3-cyclohexadienl -yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l -yl )-2- butanol and/or 4-(2,6,6-trimethyl-.l,3-cyclohexadienl-yl)-2-butyl acetate and/or 4-(6,6-dimethyl-2- methylenecyclohexen-l -yl)-2-butyl acetate or even less canbe used to impart a floral, seashore, clary sage, orrisy type scent odor to soaps, cosmetics and other products. The amount employed can range up to 80% of the fragrance components and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.

4-( 2,6,6-trimethyl- 1 ,3-cyclohexadienl -yl )-2- butanol and/or 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol and/or 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butyl acetate and/or 4-(6,6-

by the instant invention, such materials can be comdimethyl-2-methylene-3 -cyclohexe,n l-'-yl):;2-butyl acetate are useful in perfume compositions as olfactorycomponents in detergents and soaps; space odorants and deodorants; perfumes; colognes; toilet water; bath preparations such as bath oils and bath solids; hair preparations such as lacquers, brilliantines, pomades andshampoo; cosmetic preparations such as creams,

trimethyl-l,3-cyclohexadien-1-yl)-2-butanol and/or 4-(6,6 dirnefhyl-2 tne'thylene-3-cyclohexen-l-yl) 2- butanol and/or "4-'(2,6,6'-'trimethyl-l ,3-cyclohexadienl-yl') 2-butyl acetate and/or 4-(6,6-di methyl-2 methy lene '3-cyclohe'xen 'l yl)-2'-butyl acetate will suffice 'to impart a low keyed floral, seashore, clary sage, orrisy character which is one of the key odor characteristics ofmimosa and orris perfume formulations. Generally, no more than 0.5% of 4-(2,6,6-trimethyl-l ,3- cyclohexadien-l-yl)-2-butanol and/or 4-(6,6-dimethyl- 2-methylene-3-cyclohexen-l-yl)-2-butanol and/or 4- (2,6,6-trimethyl-l,3-cyclohexadien l-yl)-2-butyl acetate and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butyl acetate based on. the ultimate end product is required in the perfume composition.

In addi tion, the perfume composition or fragrance composition of this invention contains a vehicle or carrier for the 4-(2,6,6-trimethyl-1,3-cyclohexadien-l-- yl)-2-butanol and/or 4-(6,6-dimethyl-2-methylene3- cyclohexen-l-yl)-2-butanol and/or 4-(2,6,6-trimethyll,3-cyclohexadien-l-yl)-2-butyl acetate and/or 4-(6,6- dimetlfyl-2-methylene-3-cyclohexen-l-yl)-2-butyl acetate. The vehicle can be a liquid such as an alcohol, a nontoxic alcohol, a non-toxic glycol or the like. The

carrier can also be an absorbent solid such as a gum (e.g., gum arabic) or components for encapsulating the composition (such as gelatine).

It will thus be apparent that 4-(2,6,6-trimethyl-l ,3- cyclohexadien-l-yl)-2-butanol and/or 4-(6,6-dimethyl- Z-methylene-3-cyclohexen-l-yl)-2-butanol and/or 4- (2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butyl acetate and/or 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butyl acetate can be utilized to alter the sensory properties, particularly organoleptic properties such as flavor and/or fragrances of a wide variety of consumable materials.

ln'making the perfumes using the materials produced bined with auxiliary perfume ,adjuvants" including one or more of many types .of odormaterials such as bergamot oil, vetiver oil, patchouli oil, sandalwood oil, :oakmoss and floral musk The materials produced according to this invention can also be' combined with a customary perfume auxiliary adjuvants such as natural oils, synthetic oils, aldehydes, letone's, carboxylic acid esters, aryl alchols, alkanols, lactones saturated hydrocarbons, unsaturated hydrocarbons, fixatives, solvents, dispersants, surface active agents, aerosol propellants and the like;

The followingtexamples serve to illustrate embodiments of our invention as it is now. preferred to practice it. It will be understood that these examples are illustrative, and the invention is to "be considered restrictive thereto only as indicated in the appended claims.

9 EXAMPLE I Reaction:

Heat

ether One liter of diethyl ether is added to a three liter reaction flask equipped with reflux condenser, stirrer, thermometer, nitrogen purge, addition funnel and heating mantle. 10 Grams of lithium aluminum hydride is then added slowly to the diethyl ether. 130 Grams of dihy dro-a-ionone in 400 ml diethyl ether is then added to the lithium aluminum hydride-diethyl ether mass over a period of 1.5 hours. The rate of addition is adjusted to promote and continue refluxing. After the addition of other dihydro-a-ionone is complete, the reaction mass is refluxed using heat provided by a heating mantle. The reaction mass is thencooled to 5C and the eircess lithium aluminum hydrideis decomposed with 50 ml of water. I

The resulting precipitate is vacuum filtered and the aqueous layer is separated from the organic (ether) layer. The resulting organic phase is thenv washed twice with 100 ml portions of saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The ether is then evaporated yielding 110 gm. 5

residue, confirmed by IR analysis to bean alcohol having the structure:

EXAMPLE II PREPARATION OF DlHYDRO-a-IONOL ACETATE Reaction:

1 t FW To a one liter reaction flask equipped with reflux condenser, stirrer and heating mantle is added gm. of thedihydro-a-ionol produced according to the process of Example I (0.56 moles), 171 gm. of acetic anhydride i. Five 50 ml portions of 5% aqueous sodium carbonate solution; and i ii. Two 100 ml portions of saturated NaCl solution; The ether extracts are then dried over anhydrous magnesium sulfate, and evaporated leaving 121 gm. of residue, as ester having the structure: 1

EXAMPLE III PREPARATION OF DEl-IYDRODIHYDROIONOL ACETATE FROM DIHYDROIONOL ACETATE Reaction: f

(i) Dihydro-wlonol prepared according to the process of Example [1 (ii) Chloroform (iii) Quinoline 120.0 gm. (0.5 moles) 500 ml 65 m. (0. moles) The resulting mixture is cooled to 5C and 80 gm of bromine (0.5 moles) in 125 ml of chloroform is added to the reaction mass over a period of two hours, while maintaining the temperature thereof in the range of 0-5C. After bromine addition, the reaction mass is stirred for one hour at 5C and then allowed to warm up to room temperature. The chloroform solvent is then removed at reduced pressure and the resulting residue is heated using a steam bath for 3 hours, with N,N dimethylaniline. The reaction mass is then cooled and 30 ml pyridine is added. The reaction mass is then heated for a period of 30 minutes using the steam bath.

The resulting mixture is cooled and then added to a mixture of 600 ml n-pentane and 600 ml 5N hydrochloric acid. The resulting mixture now exists in two phases; an aqueous phase and an organic phase. The aqueous phase is extracted with three 100 ml portions of n-pentane. The pentane portions are combined with the organic phase and the resulting material is washed as follows:

i. Twice with 5N hydrochloric acid ii. Twice with 10% sodium bicarbonate solution iii. Twice with saturated sodium chloride solution The resulting material is then dried over anhydrous magnesium sulfate and evaporated yielding 94.3 gm of AA i1 crude. The crude materialis distilled on a microvigreaux columritat 9396C and a pressure of 0.6-0.9 mm Hg. IR, NMR; and mass spectral analyses yield the information that the material is a mixture of compounds having the structures:

The weight ratio of cyclohexadiene derivative: methy- Iene cyclohexene derivative is 65:18. This material has a woody, fruity, leathery, ionone, seashore, fatty aroma with a slight musky nuance.

EXAMPLE IV SAPONlFlCATlON OF DEHYDRODIHYDROIONOL ACETATE TO FORM DEHYDRODIHYDROIONOL Reaction:

The following materials are added to a two liter flask equipped with stirrer and thermometer:

The resulting mixture is stirred for a period of 15 hours and then neutralized with 80 ml of 5N hydrochloric acid. The ethyl alcohol is removed underreduced pressure at 50C and the reaction mass is then diluted with 200 ml of diethyl ether. The reaction mass is then washed with two 100 ml portions of saturated sodium chloride solution, after which the ether is evaporated yielding a 51.2 g of crude product. The crude product is distilled on a microvigreaux column at 89- 90C and a pressure of 0.7-1 mm Hg pressure to yield a mixture of compounds having the structures:

These structures are confirmed by GLC, mass spectral and IR analyses. The weight ratio of cyclohexadiene derivativezmethylene cyclohexene derivative is 65:18. The mixture is separableby means of GLC separation. The mixture as well as the two major individual components thereof have a leathery, green, seashore, orris, minosa, clary sage aroma with a slightly musky nuance.

EXAMPLE V ORRlS ABSOLUTE FORMULATION The following formulation is prepared:

The dehydrodihydroionol produced by the process of Example 1V imparts the main, deep, waxy, floral body of this orris absolute composition.

EXAMPLE v1 ORRIS ABSOLUTE FORMULATION The following formulation is prepared:

Ingredients Parts by Weight Dehydrodihydroionol acetate 600 Erepared by the process of xample ll p-t-amyl cyclohexanone 5O 1 -continued Ingredients Parts by Weight Methyl Ionone 75 Dibutyl sulfide 1 2-Nonenal 2 Diethyl phthalate 262 Ionone The dehydrodihydroionol acetate produced by the 0 process of Example III imparts the main, deep, waxy, floral body of this orris absolute composition.

EXAMPLE VII PERFUME FORMULATION The following mixture is prepared? The 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2- butanol imparts to this formulation a low keyed floral, seashore, clary sage, orrisy character which are included in the key odor characteristics of this type of aroma.

EXAMPLE VIII PREPARATION OF'SOAP COMPOSITION One hundred grams of soap chips are mixed with'bne gram of the perfume composition of Example VII until a substantially homogeneous composition is obtained. The perfumed soap composition exhibits a floral, seashore, clary sage, orrisy characteristic.

EXAMPLE IX PREPARATION OF A DETERGENT COMPOSITION I A total of 100 grams of a detergent powder is mixed with 0.I5 grams of the perfume composition ofExampie VII until a substantially homogeneous composition is prepared. This composition exhibits a floral, seashore, clary sage, orrisy fragrance.

EXAMPLE X XAMP E xi g PERFUMED LIQUID DETERGENT Concentrated liquid detergent with a rich mimosa character are obtainedcontaining 0.10%, 0.15%.yand

0.20% of 4-(2,6,6-trimethyl-l ,3-cyclohexadienl -yl)-2- butanol. They are prepared by adding and homogeneously mixingthe appropriate quantity of 4-(2,6,6- trimethyl;I.,3cyclohexadien-l-y-l)-2-butanol in the liquid detergent. The detergents all possess a clary sage, orris, mimosa, seashore fragrance, the intensity increasing with greater concentrations of 4-(2,6,6- trimethyl-l ,3'cyclohexadienl -yl)-2-butanol.

EXAMPLE XII COLOGNE 4-(2,6,6-Trimethyl- 1 ,3-cyclohexadien-I-yl)-2-. butanol is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handker- I chief perfume at a concentration of 5% (in 95% aquev ousethariol). A distinct and definite clary sage, orris,

mimosa, seashore fragrance is imparted to the cologne and to the handkerchief perfume.

. EXAMPLE-XIII The coinposition of Example V is incorporated in a cologne at a concentration of 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). The compo sition of Example V affords a distinct and definite strong orris fragrance to that handkerchief perfume and cologne.

EXAMPLE XIV PERFUMEFORMULATION The following mixture is prepared:

Ingredients Parts by {Weight Indol 2.0 Methyl anthranilate 2.0 n-Heptyl cyclopentanone 3,0 Grisalva (produced by the surfuric 4.0 acid treatment of 3-ethyl-l-(2,6,6- trimethyl-cyclohexen-S-yl-I )-hexen- 6,7-Dihydro-l,I,2,3.3-pentamethyl- 2.0 4-(5H) indanone (produced according to th'e'preparation of A of Swiss Patent 523,962)

Oil ofBitterOrange 5.0 Z-Qxa-l ,1,3,3-tetramethyl-2,35b, 5.0. 7,8-hexahydro- I I-I-b'enz-(O-indene Terpineol Coeur l0.0 Nerolidol I l,0.0 2-t-butyl cyclohexanyl acetate 20.0 Linalyl Acetate 90.0 Linalool, 1 I l l0.0 4-(4-methyl 4-hydroxyamyl)- A cyclo- 20.0 hexene-carboxaldehyde Benzyl alcohol I 90.0 Benzyl acetate 150.0 4-(2,6,6-trimethyl-1,3-cyclo- 3 .0

hexadienl -yl )-2-butanol The 4-(2,6,6-trimethyl-I,3-cyclohexadien-1-yl)-2- butanol imparts to the above floral type-formulation, a clary sage, orris, mimosa, seashore aroma.

EXAMPLE xy.

PERFUME FORMULATION The following mixture is prepared:

Ingredients Parts by weight Methyl anthranilate nHe tyl cyclopentanone Grisa va (produced by the 50% sulfuric treatment of 3-ethyl-l-(2,2,6-trimethylcontinued Ingredients 1 Pai'fts' by Weight cyclohexen-S-yl-l )-hexen -3-ol-6) 6,7-Dihydrol l ,2,3,3-pentamethyl- 2.0 4-(5H)-indanone (produced according v to the preparation of A of Swiss Patent 523,962)

Oil of Bitter Orange 2-Oxal l ,3,3tetramethyl-2,3 ,5 6,7,8-hexahydrol H-benz-(f)-indene Terpineol Coeur Nerolidol 2-t-butyl-cyclohexanyl acetate Linalyl Acetate Linalool 4-(4-methyl-4-hydroxyamyl)- A -cyclohexene-carboxaldehyde Benzyl alcohol Benzyl acetate 4-(6,6-dimethyl-2-methylene-3- cyclohexenl -yl)-2-butanol The 4-(6,6-dimethyl 2-methylene-3-cyc,lohexen-lyl)-2-butanol imparts to the above floral type formulation, a clary sage, orris, mimosa, seashore aroma.

EXAMPLE XVI PERFUME FORMULATION The following mixture is prepared:

Ingredients Paris by Weight The mixture of 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2-butanol and 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butanol imparts to the above floral type formulation a clary sage, orris, mimosa, seashore aroma.

EXAMPLE XVII PERFUME FORMULATION The following mixture is prepared:

Ingredients Parts by Weight Methyl Acetophenone 4 Terpineol 450 Phenyl Ethyl Alcohol 50 Bergamot Oil 20 Methyl Heptinyl Carbonate 1 Product produced according to the 20 rocess of Example III eliotropin 30 Anisic Aldehyde I80 Methyl Anthranilate 5 -continued Ingredients Parts by Weight Jasmine Absolute 3O Cinnamic Alcohol I00 Cassie Absolute l0 Hydroxycitronellal 100 The product produced by the process of Example III imparts to this formulation a woody, fruity, leathery, ionone, fatty character with a slightly musky nuance which are included in the key odor characteristics of this type of aroma.

EXAMPLE XVIII PREPARATION OF SOAP COMPOSITION One hundred grams of soap chips are mixed with one gram of the perfume composition of Example XVII until a substantially homogeneous composition is obtained. The perfumed soap composition exhibits a woody, fruity, leathery, ionone, fatty character with a slightly musky nuance.

EXAMPLE XIX PREPARATION OF A DETERGENT COMPOSITION A total of 100 grams of a detergent powder is mixed with 0.15 grams of the perfume composition of Example XVII until a substantially homogeneous composition is prepared. This composition exhibits a woody, fruity, leathery, ionone, fatty character with a slightly musky nuance.

EXAMPLE XX PREPARATION OF A COSMETIC POWDER COMPOSITION A cosmetic powder is prepared by mixing in a ball mill, 100 grams of talcum powder with 0.25 grams of the product produced by the process of Example III. It has an excellent woody, fruity, leathery, ionone, fatty character with a slightly musky nuance.

EXAMPLE XXI PERFUMED LIQUID DETERGENT Concentrated liquid detergent with a rich woody, fruity, leathery, ionone, fatty character are obtained containing 0.10%, 0.15% and 0.20% of the product produced by the process of Example III. They are prepared by adding and homogeneously mixing the appropriate quantity of the product produced by the process of Example III in the liquid detergent. The detergents all possess a woody, fruity, leathery, ionone, fatty character with a slightly musky nuance, the intensity increasing with greater concentrations of the product produced by the process of Example III.

EXAMPLE XXII COLOGNE The product produced by the process of Example III is incorporated in a cologne at a concentration of 2.5%

in aqueous ethanol; and into a handkerchief perfume at a concentration of 5% (in aqueous ethanol). A distinct and definite woody, fruity, leatherly, ionone, fatty fragrance is imparted to the cologne and to the handkerchief perfume.

What is claimed is:

1. A process for altering the organoleptic properties of a consumable material selected from the group consisting of perfumes, soaps, detergents, cosmetics, space deodorants and space odorants which comprises adding thereto a small but effective aromatizing amount of an oxo compound selected from the group consisting of 4-(2,6,6-trimethyl-l ,2-cyclohexadien-1-yl)-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2- butanol, 4,(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2- butyl acetate and 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butyl acetate.

2. A fragrance modifying composition containing an oxo compound selected from the group consisting of 4-( 2,6,6-trimethyl-l ,3-cyclohexadien- 1 -yl )-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2- butanol, 4-(2,6,6-trimethyl-l ,3-cyclohexadien-1-yl)-2- butyl acetate and 4-(6,6-dimethyl-2-methylene-3- cyclohexen-l-yl)-2-butyl acetate and an auxiliary perfume ingredient.

3. The composition of claim 2 wherein the auxiliary perfume ingredient is selected from the group consisting of natural perfume oil, synthetic perfume oil, alcohols, aldehydes, ketones, esters, and lactones.

4. A perfumed article comprising an oxo compound selected from the group consisting of 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2-butano1, 4-(6,6-dimethy]- 2-methylene-3-cyclohexen-l-yl)-2-butanol, 4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butyl acetate and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-butyl acetate and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.

5. A process for producing a perfumed composition comprising the step of admixing a composition of matter having an aroma impression which is capable of being altered with a fragrance-imparting amount of a compound selected from the group consisting of 4- (2,6,6-trimethyl-l ,3-cyclohexadienl -y] )-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-l-yl)-2- butanol, 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2- butyl acetate and 4-(6,6-dimethyl-2-methylene-3- cyclohexen-1-yl)-2-butyl acetate.

6. A cologne composition comprising an oxo compound selected from the group consisting of 4-(2,6,6- trimethyl-l,3-cyclohexadien-l-yl)-2-butanol, 4-(6,6- dimethyl-2-methylene-3-cyclohexen-l-yl)-2-butanol, 4-(2,6,6-trimethyl-l,3-cyclohexadien-l-yl)-2-butyl acetate, 4-(6,6-dimethyl-Z-methylene-3-cyclohexen-lyl)-2-butyl acetate, ethanol and water.

7. The process of claim 1 wherein the oxo compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2- butanol.

8. A process according to claim 7 wherein the consumable material is a soap, detergent, cosmetic, space deodorant, space odorant, or perfume composition.

9. The composition of claim 6 wherein the oxo compound is 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2- butanol.

10. The perfumed article of claim 4 wherein the oxo compound is 4-(2,6,6-trimethyl-l,3-cyclohexadien-lyl)-2-butanol and a detergent, soap, bath preparation, hair preparation, cosmetic preparationor powder.

11. The process of claim 5 wherein the oxo compound is 4-(2,6,6-trimethyl-l ,3-cyclohexadien-l-yl)-2- butanol.

12. The cologne composition of claim 6 wherein the oxo compound is 4-(2,6,6-trimethyl-l,3-cyclohexadien- 1 -yl)-2-butanol. 

1. A process for altering the organoleptic properties of a consumable material selected from the group consisting of perfumes, soaps, detergents, cosmetics, space deodorants and space odorants which comprises adding thereto a small but effective aromatizing amount of an oxo compound selected from the group consisting of 4-(2,6,6-trimethyl-1,2-cyclohexadien-1-yl)-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol, 4,(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate.
 2. A FRAGRANCE MODIFYING COMPOSITION CONTAINING AN OXO COMPOUND SELECTED FROM THE GROUP CONSISTING OF 4-(2,6,6TRIMETHYL-1,3-CYCLOHEXADIEN-LYL)2-BUTANOL, 4-(2,6,6YL-2-METHYLENE-3-CYCLOHEXADIEN-1-YL)2-BUTANOL, 4-(6,6TRIMETHYL-1,3-CYCLOHEXADIEN-1-YL)-2-BYTYL ACETATE AND 4-(2,6,6DIMETHYL-2-METHYLENE-3-CYLOHEXEN-2-YL)-2-BUTYL ACETATE AND AN AUXILIARY PERFUME INGREDIENT.
 3. The composition of claim 2 wherein the auxiliary perfume ingredient is selected from the group consisting of natural perfume oil, synthetic perfume oil, alcohols, aldehydes, ketones, esters, and lactones.
 4. A perfumed article comprising an oxo compound selected from the group consisting of 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol, 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-butyl acetate and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.
 5. A process for producing a perfumed composition comprising the step of admixing a composition of matter having an aroma impression which is capable of being altered with a fragrance-imparting amount of a compound selected from the group consisting of 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol, 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate and 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate.
 6. A cologne composition comprising an oxo compound selected from the group consisting of 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butanol, 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butyl acetate, 4-(6,6-dimethyl-2-methylene-3-cyclohexen-1-yl)-2-butyl acetate, ethanol and water.
 7. The process of claim 1 wherein the oxo compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol.
 8. A process according to claim 7 wherein the consumable material is a soap, detergent, cosmetic, space deodorant, space odorant, or perfume composition.
 9. The composition of claim 6 wherein the oxo compound is 4-(2, 6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol.
 10. The perfumed article of claim 4 wherein the oxo compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol and a detergent, soap, bath preparation, hair preparation, cosmetic preparation or powder.
 11. The process of claim 5 wherein the oxo compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol.
 12. The cologne composition of claim 6 wherein the oxo compound is 4-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-butanol. 